Ketoximes and other oxygenated amine compounds are increasingly important intermediates for chemical manufacture. The art has appreciated the desirability of being able to produce ketoximes and hydroxylamines from the corresponding amines, and a suggested procedure involves using hydrogen peroxide in an aqueous system. Although this system may give little or no by-products, a major problem is the relatively high cost of this oxidizing agent. Organic hydroperoxides have not been regarded as feasible for such a process and they might be expected to form troublesome by-products. The art is confronted by the problem of providing processes for producing hydroxylamines and oximes from corresponding primary amines in a convenient and economic manner.
This invention provides an answer to the problem of producing oximes or hydroxylamines in an economical fashion while conserving or improving essential raw material values.
The discoveries associated with the invention and relating to the solution of the above problems, and other objects achieved in accordance with the invention as set forth herein include the provision of:
A process for preparing an oxygenated amine such as an oxime or a hydroxylamine from the corresponding primary amine; the amine group being attached to a primary or secondary carbon atom, which process comprises treating the amine with a combination of (1) a dissolved metal catalyst of the group consisting of peracid forming or hydroxylation catalysts (i.e. compounds of Ti, V, Cr, Se, Zr, Nb, Mo, Te, Ta, W, Re, and U) and (2) an organic hydroperoxide as the essential oxidizing agent; (the amount of oxidizing agent being in the range of 0.01 to 10 mols per mol of the amine, and the amount of metal being in the range of 0.00001 to 0.1 mols per mol of the hydroperoxide, preferably); PA1 Such a process wherein the temperature is in the range of about -10.degree. to +175.degree.C.; PA1 such a process wherein cyclohexanone oxime is prepared using cyclohexyl hydroperoxide; PA1 Such a process wherein cyclohexanone oxime is prepared using cumene hydroperoxide, or a hydroxy-hydroperoxide; PA1 Such a process wherein the catalyst is a molybdenum compound; PA1 Such a process wherein the catalyst is a vanadium compound; PA1 Such a process wherein the amine group is attached to a secondary carbon atom of a cycloalkyl group having 4 to 16 carbon atoms; PA1 Such a process wherein the hydroperoxide is prepared by reacting gaseous oxygen with ethylbenzene in the presence of an oxidation initiator, the amine has 1 to 20 carbon atoms, and by-product alpha-phenylethanol is recovered; PA1 such a process wherein the unreacted ethylbenzene is recycled to the hydroperoxide preparation step; PA1 such a process wherein the alpha-phenylethanol is dehydrated to form styrene; PA1 such a process wherein the dehydration step is in the vapor phase over titania catalyst at a temperature in the range of 180.degree. to 280.degree. C. PA1 such a process wherein a catalytic amount of molybdenum disulfide is the catalyst; PA1 such a process wherein the alpha-phenylethanol is dehydrogenated to form acetophenone, and the latter is recovered; PA1 such a process wherein the alpha-phenylethanol is hydrogenated to ethylbenzene, and the latter is used forming its hydroperoxide; PA1 such a process wherein the hydroperoxide is prepared by reacting gaseous oxygen with cumene in the presence of an oxidation initiator, the amine has 1 to 20 carbon atoms, and by-product cumyl alcohol is recovered; PA1 such a process wherein a catalytic amount of a molybdenum salt of a carboxylic acid is the catalyst; PA1 such a process wherein the cumyl alcohol is converted to cumene, and the latter is used to form its hydroperoxide; PA1 such a process wherein the cumyl alcohol is converted to alpha-methyl styrene; PA1 such a process wherein n-hexylaldoxime is prepared from n-hexylamine; PA1 such a process wherein a hydroxylamine is prepared from the corresponding amine; PA1 such a process wherein cyclohexylhydroxylamine is prepared; PA1 and other objects which will be apparent as details or embodiments of the invention are set forth hereinafter.